Bicyclo{8 2.2.1{9 {0 Hept-5(6)-yl compounds

ABSTRACT

2-Vinylbicyclo(2.2.1)hept-5(6)-yl and 2epoxyethylbicyclo(2.2.1)hept-5(6)-yl compounds, wherein the vinyl compounds are prepared by the addition of the active hydrogencontaining compounds to the strained-ring double bond of the bicyclo-heptene ring in 2-vinylbicyclo(2.2.1)hept-5-ene and the epoxy compounds are prepared by the epoxidation of the vinyl compounds. The compounds find utility as solvents for resins and oils, monomers for preparing synthetic waxes and resins, chemical intermediates for pharmaceuticals, wetting agents, insecticides, emulsifying agents, detergents, bactericides and fungicides.

United States Patent Rick et al.

BICYCLO[2.2.1] HEPT-5(6)-YL COMPOUNDS Inventors: Edward A. Rick,Charleston, W. Va.; Samuel W. Tinsley, Darien, Conn.

Assignee: Union Carbide Corporation, New

York, NY.

Filed: May 27, 1971 Appl. No.: 147,650

Related US. Application Data Division of Scr. No. 677,741, on. 24, 1967,Pat. No.

3,646,l 13, which is a continuation-in-part of Ser. No. 404,477, Oct.16, 1964, Pat. No. 3,459,775.

US. Cl. 260/611 F; 260/617 F Int. Cl. C07C 35/28; C07C 43/18 Field ofSearch 260/617, 611 F, 617 F References Cited UNITED STATES PATENTS6/1961 Cohcn 260/617 F Primary ExaminerPaul M. Coughlan, Jr. AssistantExafninerD. B. Springer Attorney, Agent, or Firm-Francis M. Fazio [57]ABSTRACT 2-Vinylbicyclo[2.2.1]hept-5(6)-yl and2-epoxyethylbicyclo[2.2.l]hept-5(6)-yl compounds, wherein the vinylcompounds are prepared by the addition of the active hydrogen-containingcompounds to the strained-ring double bond of the bicyclo-heptene ringin 2-vinylbicyclo[2.2.1]hept-5-ene and the epoxy compounds are preparedby the epoxidation of the vinyl compounds. The compounds find utility as$01- vents for resins and oils, monomers for preparing synthetic waxesand resins, chemical intermediates for pharmaceuticals, wetting agents,insecticides, emulsifying agents, detergents, bactericides andfungicides.

3 Claims, No Drawings BICYCLO[2.2.1] HEPT-5(6) -YL COMPOUNDS 3 ,646,l13, which in turn was a divisional application of application Ser. No.404,477 filed Oct. 16, 1964, now US. Pat. No. 3,459,775.

This invention relates to a novel class of 2-vinyland2-epoxyethylbicyclo[ 2.2. l ]hept-S 6 )-yl compounds, and to a methodfor their. preparation. In one aspect, this invention relates to a novelsub-class of 2-vinylbicyclo[2.2.l]hept-5(6)-yl compounds, 7 and to amethod for their preparation. In another aspect, this invention relatesto a novel sub-class of 2-epoxyethylbicyclo[2.2.l]hept-5(6)-ylcompounds, and to a method for'their preparation. i

It has. now been discovered that a heretofore unknown class of2-vinyland 2-epoxyethylbicyclo[2.2.l- ]hept-5(6)-yl compunds can beprepared from 2-vinylbicyclo[2.2.l]hept-5rene. In particular, it hasbeen found-that a variety of compounds containing active hydrogen atomsas defined hereinafter can be readily added to the strained-ring doublebond of the bicycloheptene ring in 2-vinylbicyclo[2.2.l]hept-S-ene toproduce a novelsub-class of 2-vinylbicyclo[2,2.l ]hept- 5(6)-ylcompounds. Moreover, it also has been found that these2-vinylbicyclo[2.2.l ]hept-5(6)-yl compounds'can be epoxidated toproduce a still further novel subclass of2-epoxyethylbicyclo[2.2.l]hept- 5(6)-yl compounds. I I

, Accordingly, it is an object of this invention to provide a novelclass of 2-vinyland 2-epoxyethylbicyclo[2.2.l ]hept-5(6)-yl compounds.It is a specific object to provide a novel sub-class of2-vinylbicyclo[2.2. l ]hept-5(6)-yl compounds. It is a further specificobject to provide a .novel sub-class of2-epoxyethylbicyclo[2.2.l]hept-5(6)-yl compounds. It is yet anotherobject to provide a novel sub-class of2-epoxyethylbicyclo[2.2.l]hept-5(6)-yl vicinal epoxides. It is .yet afurther object to provide novel 2-vinylbicyclo[2.2.l]hept-5(6)-ylesters, 1 2-vinylbicyclo[2.2.l- ]hept-5(6)-yl ethers,2-epoxyethylbicyclo[2.2.l ]hept- 5(6 )-yl esters,2-epoxyethylbicyclo[2.2. l ]hept-5(6)-yl ethers, and the like. It isstill another object to provide novel bis( 2-vinyland2-epoxyethylbicyclo[2.2. l ]hept- 5(6)-yl compounds, tris (2-vinyland2-epoxyethylbicyclo[2.2.1]hept-5(6)-yl compounds and tetra(2- vinyland2-epoxyethylbicyclo[2.2.l]hept-5(6)-yl compounds. It is yet anotherobject to provide a novel method for the preparation of the 2-vinyland2-epoxyethylbicyclo[2.2.l ]hept-5(6)-yl compounds as disclosed herein.These and other objects of this invention will become apparent to thoseskilled in the art to which this invention pertains from the ensuingdescription thereof.

In a broad aspect, the novel class of 2-vinyland2-epoxyethylbicyclo[2.2.l ]hept-5(6)-yl compounds of this invention canbe represented by formula (I):

wherein n has a value of from 0 to 3, inclusive; R is the residueremaining after the loss of only active hydrogen from an activehydrogen-containing compound, or the vicinal epoxy derivative of saidresidue when n is O; and each R is either the vinyl group (-CH CH or theepoxyethyl group (CH-CH2) The preferred form of the 2-vinyland2-epoxyethylbicyclo[2.2.1]hept-5(6)-yl compounds represented by formula(I), are those wherein n is O or 1, and R and each R are as hereinabovedefined with reference to formula (I).

As used herein, the term residue is meant that portion of a compound,containing from one to four active hydrogen atom(s), which remains afteronly the loss of said active hydrogen atom(s) from said compound, said'portion of which adds to the double bond in the bicycloheptene ring of2-vinylbicyclo[2.2.l- ]hept-S-ene. The residue may be mono-, di-, tri-,or tetravalent, depending upon the number of hydrogen atoms lost by theactive hydrogen-containing compound. The term active hydrogen-containingcompound as used herein refers to compounds having a replaceablehydrogen atom attached -to either oxygen, sulfur, or halogen atoms, asdisclosed herein. It does not refer to hydrogen atoms attached tonitrogen or other atoms, except as disclosed herein. The term activehydrogen-containing compound as defined herein includes acids, alcohols,glycols, water, hydrogen halides, isothiocyanic acid, and geminaldihydroxy compounds wherein a hydrogen atom is attached to eitheroxygen, sulfur or halogen atoms, as disclosed herein. It does notinclude, for example, acetylene, amines, amides, or sulfinic acids. Bythe term vicinal epoxy is meant a cyclic three membered etherolefinically unsaturated tetrabasic acids; saturated or olefinicallyunsaturated partial-acid esters of tetrabasic acids, isothiocyanic acid;hydrogen halides; alcohols such as, saturated or olefinicallyunsaturated aliphatic or alicyclic monoalcohols; saturated orolefinically unsaturated aliphatic diols, triols and tetraols; phenols;saturated or olefinically unsaturated aliphatic or alicyclic mercaptans;thiophenols; water; and the like. In addition, the foregoing residuescan be substituted with simple substituents such as, for example, halo,hydroxy, cyano, thio, nitro, and like groups.

In particular, with reference to formula (I), when n is O to 3,inclusive, illustrative R residues include among others, the residuesof, for example, saturated alilphatic monocarboxylic acids of from 1 to20 carbon atoms, such as, for example, formic, acetic, propionic,butyric, isobutyric, valeric, isovaleric, hexanoic, heptanoic, octanoic,nonanoic, decanoic, undecanoic, dodecanoic, tetradecanoic, hexadecanoic,heptadecanoic, octadecanoic, and the like; olefinically unsaturatedaliphatic monocarboxylic acids of from 3 to 20 carbon atoms, such as,for example acrylic, 3-butenoic, methacrylic, crotonic, 2,4-hexadienoic,oleic, elaidic, linoleic, linolenic, and the like, saturated aliphaticdi-, tri-, and tetracarboxylic acids, of from 2 to 12 carbon atoms suchas, for example oxalic, malonic, succinic, glutan'c, adipic, pirnelic,suberic, azelaic, sebacic, l,2,3- propanetricarboxylic,l,2,3,4-butanetetracarboxylic, and the like. olefinically unsaturatedaliphatic di-, tri, and tetracarboxylic acids of from 4 to carbon atomssuch as, for example, maleic, fumaric, itaconic, and the like; alicyclicacids of from 4 to 20 carbon atoms such as, for example,cyclopropanecarboxylic, cyclopentanecarboxylic, hydrocarpic,chaulmoogric, hexahydrobenzoic, 2,3,4,5-tetrahydrobenzoic, abietic,carnphoric, hexahydrophthalic, and the like; aromatic monocarboxylicacids of from 7 to carbon atoms such as, for example, benzoic,l-naphthoic, o-toluic, phenylacetic, and the like; aromatic diandpolycarboxylic acids of from 8 to 16 carbon atoms such as, for example,phthalic, isoph thalic, terephthalic, ophenylenediacetric, l,2,3,4-,1,2,3,5- and l,2,4,5-benzenetetracarboxylic, and the like; substitutedaliphatic acids of from 2 to 12 carbon atoms such as, for example,glycolic, lactic, gluconic, malic, tartaric, citric, chloroacetic,a-bromobutyric, thioglycolic, cyanoacetic, and the like; substitutedaromatic acids of from 7 to 14 carbon atoms such as for example,o-chlorobenzoic, o-nitrobenzoic, 3,5-dinitrobenzoic, salicyclic,mhydroxybenzoic, gallic, mandelic, and the like; saturated aliphaticmonohydroxy alcohols of from 1 to 18 carbon atoms such as, for example,methanol, ethanol, l-propanol, 2-propanol, l-butanol,2-methyl-lpropanol, Z-butanol, 2-methyl-2-propanol, l-pentanol,3-methyl-l-butanol, 2-methyl-2-butanol, 2-pentanol, 3-pentanol,l-hexanol, l-heptanol, l-octanol, 2- octanol, l-nonanol, l-dodecanol,l-octadecanol, and the like; olefinically unsaturated aliphaticmonohydroxy alcohols of from 3 to 20 carbon atoms such as, for example,allyl alcohol, propargyl alcohol, crotyl alcohol, oleyl alcohol,citronellol, geraniol, linoleyl alcohol, and the like; oxyalkyleneglycol monoethers,

wherein A is alkyl of from 1 to 18 carbon atoms, B is hydrogen, methylor ethyl and m has a value of from 1 to 4; saturated aliphatic dihydroxyalcohols of 2 to 18 carbon atoms such as, for example, ethylene glycol,propylene glycol, trimethylene glycol, 2,3-butylene glycol,tetramethylene glycol, sym-dimethylethylene glycol, hexamethyleneglycol; polyoxyalkylene glycols such as diethylene glycol, triethyleneglycol, tetra-, pentaetc. ethylene glycols, di-, tri-, tetra-, etc.propylene glycols and butylene glycols and the like; saturatedalliphatic polyhydroxy alcohols of from 3 to 10 carbon atoms such as,for example, glycerol, trimethylolpropane, pentaerythritol, mannitol,sorbitol, and the like; alicyclic alcohols of from 5 to 28 carbon atomssuch as, for example, cyclopentanol, cyclohexanol, 2-methylcyclohexanol, menthol, borneol, cholesterol, ergosterol, isosotel, andthe like; araliphatic alcohols of from 7 to 16 carbon atoms such as, forexample, benzyl alcohol, 2-phenylethyl alcohol, benzhydrol,triphenylcarbinol, cinnamyl alcohol, salicyl alcohol, coniferyl alcohol,and the like; phenols such as phenol, 2,6-di-tertbutyl-4-methylphenol,2,6-di-tert-butylphenol, 2,2- bis(p-hydroxyphenyl)propane, and the like.

In general, with reference to formula (I), illustrative vicinal epoxyderivatives of R include, among others, the vicinal epoxides ofolefinically unsaturated aliphatic or alicyclic acids; olefinicallyunsaturated dibasic acids; olefinically unsaturated half-acid esters ofdibasic acids; olefinically unsaturated tri-and tetrabasic acids;olefinically unsaturated partial-acid esters of triand tetrabasic acids;olefinically unsaturated aliphatic or alicyclic alcohols, olefinicallyunsaturated aliphatic polyols, and the like. In addition, the foregoingvicinal epoxy derivatives of R can be substituted with simplesubstituents such as, for example, halo, hydroxy, cyano, nitro, and likegroups.

In particular, with reference to formula (I), illustrative vicinal epoxyderivatives of R include, among others, the epoxides of olefinicallyunsaturated aliphatic monocarboxylic acids of from 3 to 19 carbon atomssuch as, for example, acrylic acid, 3-butenoic acid, methacrylic acid,crotonic acid, oleic acid, linolenic acid, and the like; olefinicallyunsaturated aliphatic mmonohydroxy alcohols of from 3 to 18 carbon atomssuchas, for example, allyl alcohol, propargyl alcohol, crotyl alcohol,oleyl alcohol, citronellol, geraniol, linolenyl alcohol, and the like.

Illustrative specific 2-vinyland 2-epoxyethyl bicyclo[2.2.l]hept-5(6)-yl compounds within the novel class encompassed by formula(I), include, among others, 2-vinylbicyclo[2.2.l]hept-5(6)-yl acetate,2-epoxyethylbicyclo[2.2.l]hept-5(6)-yl acetate,2-vinylbicyclo[2.2.l]hept-5(6)-yl propionate, 2-epoxyethylbicyclo[2.-2.l]hept-5(6)-yl propionate, 2-vinylbicyclo[2.2.1]hept-5(6)-yl butyrate,2-epoxyethylbicyclo[2.2.l ]hept-5(6)-yl butyrate, 2-vinylbicyclo[2.2.l-

]hept-5 6 )-yl valerate, 2-epoxyethylbicyclo 2.2. l hept-5( 6 )-ylvalerate, 2-viny1bicyclo[ 2.2. l lhept- 5 6 )-y] hexanoate,2-epoxyethylbicyclo[ 2.2. 1 ]hept- 5(6)-yl hexanoate,2-vinylbicyclo[2.2.l]hept-5(6)-yl heptanoate, 2-epoxyethylbicyclo[ 2.2.l ]hept-5(6)-yl heptanoate, 2-vinylbicyclo[2.2.l]hept-5(6)-yl octanoate,2-epo xyethylbicyclo[ 2.2. 1 ]hept-5 6)-yl octanoate,2-vinylbicyclo[2.2.l ]hept-5(6)-yl nonanoate, 2-epoxyethylbicyclo[ 2. 2.l ]hept-5 6 )-yl nonanoate, 2-vinylbicyclo[ 2.2. l ]hept-5(6 )-yldecanoate, 2-epoxyethylbicyclo[ 2 .2. 1 ]hept-5 6 )-yl decanoate,2-vinylbicyclo[2.2.l]hept-5(6)-yl hexadecanoate, 2-epoxyethyl- R iseither alkylene of from 1 to 18 carbon atoms, alkenylene of from 4 to 20carbon atoms, cycloalkylene of from 5 to 12 carbon atoms,cycloalkenylene of from 5 to 12 carbon atoms, or arylene of from 6 to 10carbon atoms; and R is either alkylene of from 1 to 18 Carbon atoms,alkenylene of from 2 to 20 carbon atoms; cycloalkylene of from 5 to 12carbon atoms, cycloalkenylene of from 5 to 12 carbon atoms, or aryleneof from 6 to 10 carbon atoms; R is either hydrogen, alkyl of from 1 to18 carbon atoms, alkenyl of from 2 to 20 carbon atoms, cycloalkyl offrom 5 to 12 carbon atoms, cycloalkenyl of from 5 to 12 carbon atoms,and aryl of from 6 to 10 carbon atoms; Y is either hydrogen, methyl orethyl; and x is an integer of from 1 to 5, inclusive.

Highly preferred 2-vinylbicyclo[2.2.1]hept-5(6)-yl compounds representedby formula (III), are those represented by formula (IV):

CH CH 8 wherein R is either HO-, HS, I-ICOO, -NCS, R S R O, R COOor ROCC-R -COO-; R is either alkyl of from 1 to. 18 carbon atoms, alkenyl offrom 2 to carbon atoms, cycloalkyl of from 5 to 12 carbon atoms,cycloalkenyl of from 5 to 12 carbon atoms or aryl of from 6 to 10 carbonatoms; and R is either alkylene of from 1 to 18 carbon atoms, alkenyleneof from 2 to 20 carbon atoms, cycloalkylene of from 5 to 12 carbonatoms, cycloalkenylene of from 5 to 12 carbon atoms, or arylene of from6 to 10 carbon atoms.

Highly preferred 2-vinylbicyclo[2.2.l]hept-5(6)-yl compounds representedby formula (V) are those represented by formulae (VI) and (VII):

(VII) 2.

R coo wherein each R is alkenyl of from 2 to 20 carbon atoms, preferablyalkenyl of from 2 to 4 carbon atoms. Illustrative alkenyl groups of from2 to 20 carbon atoms CH CH wherein R is alkylene of from 1 to 20 carbonatoms, preferably alkylene of from 2 to 4 carbon atoms. Illusinclude,for example, vinyl, allyl, isopropenyl, 3-butenyl, 4-.pantenyl,S-hexenyl, 6-heptenyl, 7-octenyl, 3-

trative alkylene groups of from 1 to 20 carbon atoms nonenyl, 9-decenyl,l7-octadecenyl, and the like.

include, for example, methylene ethylene, trimethylene, tetramethylene,pentamethylene, hexamethylene, heptamethylene, octamethylene,nonamethylene, decamethylene, octadecamethylene, alkyleneoxyalkylenesIllustrative 2-vinylbicyclo[2.2. 1 ]hept-5( 6)-yl compounds encompassedwithin the sub-class represented by formula II) include, among others,the 2-vinylbicyclo[2.2;1]hept5(6)-yl esters such as, 2-vinylbicysuch asethyleneoxyethylene, propyleneoxybutylene clo[2.2.1]hept-5(6)-ylacetate, 2-vinylbicyclo[2.2.l-

]hept-S 6 )-yl propionate, 2-vinylbicyclo 2. 2. 1 ]hept- 5(6)-ylbutyrate, 2-vinylbicyclo[2.2. 1 ]hept-S 6)-yl valerate, 2-vinylbicyclo[2 .2. 1 ]hept-5( 6 )-yl hexanoate, 2-vinylbicyc1o 2. 2. 1 ]hept-5 6 )-ylheptanoate, bis( 2- vinylbicyclol 2.2. l ]hept-5(6)-yl) oxalate, bis(2-vinylbicyclo[2.2.1 ]hept-5( 6 )-yl) malonate, bis( 2-vinylbicyclo[2.2.l ]hept-5( 6)-yl) succinate, tris( 2-vinylbicyclo[2.2 l ]hept-5( 6)-yl)aconitate, 2-viny1bicyclo[2.2. I ]hept5(6)-yl formate,2-vinylbicyclo[2.2. 1- ]hept-5( 6 )-yl bromide, 2-vinylbicyclo[ 2.2. 1]hept- 5(6)-y1 isothiocyanate, 2-vinylbicyclo[2.2.1 ]hept- 5(6)-ylacrylate, 2-vinylbicyclo[2.2.1]hept-5(6)-yl methacrylate, and the like;the 2-vinylbicyclo[2.2.l- ]hept-5(6)-yl ethers such as. 2-vinylbicyclo[22.l- ]hept-5(6)-yl methyl ether, 2-vinylbicyclo[2.2.l]hept- 5(6)-ylethyl ether, 2-vinylbicyclo[2.2.1]hept-5(6)-yl propyl ether,2-vinylbicyclo[2.2.l]hept-5(6)-yl butyl ether, propylene glycolbis(2-vinylbicy'clo[2.2.Ijhept- 5(6)-yl) ether, trimethylene glycolbis(Z-vinylbicyclo[2.2.l]hept-5(6)-yl) ether, glycerol tris(2-vinylbicyclo[2.2. I ]hept-5(6)-yl) ether, ethylene glycol bis(-2vinylbicyclo[2.2. 1 ]hept-5( 6)-yl) ether, bis(2-vinylbicyclo[2.2.l]hept-5(6)-yl) ether, and the like; and alcoholssuch as 2-vinylbicyclo[2.2.l]heptan-5(6)-ol, ethylene glycol mono(bicyclo[2.2. 1 ]hept-5( 6)-yl) ether, and the like.

Another novel sub-class of 2-vinyland 2-epoxyethylbicyclo[2.2. l]hept-5( 6)-yl compounds of this invention are the2-epoxyethylbicyclo[2.2.1]hept-5(6)-yl 5 compounds which can berepresented by formula (VIII):

R is either alkylene of from 1 to 18 carbon atoms cycloalkylene of from5 to 12 carbon atoms, or arylene of from 6 to 10 carbon atoms; R iseither alkylene of from 1 to 18 carbon atoms, alkenylene of 2 carbonatoms, cycloalkylene of from 5 to 12 carbon atoms, and arylene of from 6to 10 carbon atoms; R is either hydrogen, alkyl of from 1 to 18 carbonatoms, cycloalkyl of from 5 to 12 carbon atoms, and aryl of from 6 to 10carbon atoms; Y is either hydrogen, methyl or ethyl; and x is an integerof from I to 5, inclusive.

Highly preferred 2-epoxyethylbicyclo[2.2.l]hept- 5(6)-yl compoundsrepresented by formula (IX) are. those represented by formula (X):

X) Y V CH *CH 3 CH CH wherein R is alkylene of from I to carbon atoms,preferably 2 to 4 carbon atoms.

Particularly preferred 2 -epoxyethylbicy ,clo[2.2.l ]hept-5(6)-ylcompounds represented by formula (VIII) are those represented by formula(XI):

- is T 2 wherein R is the residue remaining after the loss of onlyactive hydrogen from an active hydrogen-containing compound and n is avalue of O, I, 2, or 3, inclusive.

particularly preferred 2-epoxyethylbicyclo[2t2.l- ]hept-5(6)-ylcompounds encompassed by formula (VIII), are those represented byfonnula (IX):

1 1 wherein R is either I-IO, I-ICOO, R SO R O, R COO, or ROOC-R COO; Ris either alkyl of from 1 to l8 carbon atoms, epoxyalkyl of from 3 to 20carbon atoms wherein the epoxide moeity o l Q is at least one carbonatom removed from the SO or ether O atoms, cycloaklyl of from 5 to 12car- 10 bon atoms, epoxycycloalkyl of from '5 to 12 carbon atoms whereinthe epoxide moiety is at least one carbon atom removed from the SO orether O atoms, or aryl of from 6 to 10 carbon atoms; R is eitheralkylene of from 1 to 18 carbon atoms or C=C. I] H epoxyalkylene of from4 to 20 carbon atoms wherein the epoxide moiety is at least one carbonatom re moved from both OOC moieties, apoxycycloalkylene of from 5 to 12carbon atoms wherein the epoxy moiety is at least one carbon atomremoved from both of the -OOC moieties, and arylene of from 6 to l0carbon atoms; R is either alkyl of from 1 to 18 carbon atoms, vinyl,

epoxyalkyl of from 3 to 20 carbon atoms wherein the epoxy moiety is atleast one carbon atom removed from the COO moiety, cycloalkyl of from 5to 12 carbon atoms, epoxycycloalkyl of from 5 to 12 carbon atoms whereinthe epoxy moiety is at least one carbon atom removed from the COOmoiety, and aryl of from 6 40 to 10 carbon atoms; R is either alkyl offrom 1 to 18 carbon atoms, cycloalkyl of from 5 to 12 carbon atoms,epoxyalkyl of from 3 to 20 carbon atoms wherein the epoxy moiety is atleast one carbon atom removed from the OOC moiety, epoxycycloalkyl offrom 5 to 12 carbon atoms wherein the epoxy moiety is at least onecarbon atom removed from the OOC- moiety, and aryl of from 6 to 10carbon atoms; and R is either hydrogen or alkyl of from 1 to 5 carbonatoms.

Highly preferred 2-epoxyethyl bicyclo[2.2.l1hept- 5(6)-yl compoundsrepresented by formula (VIII), are those represented by formulae (XII)and (XIII):

5 6 )-yl propionate, 2-epoxyethylbicyclo 2. 2. l ]hept- 5 6 )-ylbutyrate, 2-epoxyethylbicyclo 2. 2.1 ]hept- 5(6)-yl valerate,2-epoxyethylbicyclo[2.2.l ]hept- 5 6 )-yl hexanoate,2-epoxyethylbicyclo[ 2 2.1 ]hept- 5(6)-yl heptanoate,bis(2-epoxyethylbicyclo[2.2. l-

]hept-5(6)-yl)maleate and the like; the 2-epoxyethylbicyclo[2.2. l]hept-5(6)-yl ethers such as, 2-epoxyethylbicyclo[2.2.l]hept-5(6)-ylethyl ether, 2-epoxyethylbicyclo[2.2. l ]hept-5(6)-yl propyl ether,2-epoxyethylbicyclo[2.2.l]hept-5(6)-yl glycidyl ether, propylene glycolbis(2-epoxyethylbicyclo[2.2.l]hept- 5(6)-yl) ether, trimethylene glycolbis(2-epoxyethylbicyclo[2.2. l ]hept-5( 6)-yl) ether, glycerol tris(2-epoxyethylbicyclo[2.2. 1 ]hept-5(6)-yl ether, and the like.

In general, the compounds of this invention can be prepared in twosteps. In the first step, the 2-vinylbicyclo[2.2. l ]hept-5(6)-ylcompounds are prepared by the addition of a compound containing anactive hydrogen atom as defined hereinabove to the 2-vinylbicyclo[ 2.2.l ]hept-S-ene. The 2-vinylbicyclo[2.2.l ]hept- 5-ene starting materialcan be prepared in good yields by the condensation of cyclopentadienewith butadiene according to the method disclosed in Chemical Abstracts,53, 4232d (1959).

In many instances it is preferable to carry out the addition reaction inthe presence of an acid catalyst. Some acid catalyst is necessary exceptwhere the active hydrogen compound is itself acidic (i.e., formic acid,trichloroacetic acid, and the like. The acid catalysts which can beemployed include, among others, sulfuric acid, boron trifluoride,organic sulfonic acids, for example benzene sulfonic acid, or methylsulfonic acid; coordination complexes of boron trifluoride withoxygenated compounds such as ethers, as BF O(C H .carboxylic acids, asBF .2CI-I COOH; alcohols, as (BF )2C I-I OI-I; ketones such as BF .CIICOCH and water, such as BF .I-I O BF .2H O; acidic ion exchange resins(insoluble acidic materials) i.e., Amberlites and Zeolites; silicates;and Dowex resins; furthermore, the halides of amphoteric metals such aszinc chloride, stannic chloride, titanium tetrachloride, antimonychloride, aluminum chloride, or ferric chloride may be used as catalystsin the process of this invention. The amount of catalyst which can beemployed ranges from about 0.0001 to about 25% by weight of2-vinylbicyclo[2.2.l ]hept-S-ene with a range of from about 2 to about10% being preferred.

The temperature at which the first step can be carried out successfullyranges from room temperature or below to about 250C, with a range offrom about C. to about C. being preferred. An excess of the activehydrogen-containing compound is generally em- CH CH ployed but is notessential. The amount of active hydro gen-containing compounds employedoften depends upon the particular addition product desired, so it canvary within wide limits. The pressure employed in the first step of theprocess of this invention can be atmospheric, subatmospheric orsuper-atmospheric, with atmospheric being preferred.

In carrying out the first step of the process of this invention, it ispreferred that the 2-vinylbicyclo[2.2. l

hept-S-ene be added slowly to an excess of the activehydrogen-containing compound in the presence of an acid catalyst. Inthis way, residue formation is minimized. In addition, it is sometimespreferable to carry out the addition reaction in the presence of a freeradi- 5 cal inhibitor in order to minimize polymerization of, forexample, the ester addition products such as, the acrylates andmethacrylates which readily polymerize. Distillation of the acrylates,methacrylates and other sensil tive products is preferably carried outunder very high vacuum and in such a manner that both the liquid and thevapors are in contact with a free radical inhibitor at all times. Thisis best accomplished by passing a very slow stream of nitric oxidethrough the system. Suitable free radical inhibitors include, amongother, nitric oxide, hydroquinone, hydroquione monomethyl ether, and thelike.

It is to be noted that this invention intends to encompass thederivatives of the hydrate of 2-viny1bicyclo [2.2.1]hept--ene, that is,2-vinylbicyclo[2.2.1]heptan-5(6)-ol (Example IX) such as, the bis-ether,the carbonate, and the acetals.

In the second step of the process of this invention, the2'epoxyethylbicyclo[2.2.l]hept-5(6) -yl compounds. generally areprepared by the epoxidation of said 2- vinylbicyc1o[2.2. l ]hept-5(6)-ylcompounds. In this step, the vinyl group on the number 2-ring position(2-vinyl) is epoxidized, or the olefinic double bond(s) in the residueon the -5(6) ring positions of the 2-vinylbicyclo[2.2.l ]hept-5(6)-ylcompound, is epoxidized or both.

The epoxidizing agents suitable in the second step are active oxygenagents such as, for example hydrogen peroxide, the organic paracids,metal-activated hydrogen peroxide, alkaline hydrogen peroxide, and thelike. The amount of epoxidizing agent can range from less thanstoichiometric amounts to greater than stoichiometric amounts, with a 5to 10% excess generally being preferred. Of course, the amount ofepoxidizing agent depends upon the final product-desired, i.e.,monoepoxide, diepoxide, and so forth, so it, of course, can vary withthe amount of epoxidation desired. The preferred epoxidizing agent isperacetic acid.

The temperature of the epoxidation reaction can range from about 0C. toabout 100C., with a temperature range of from about 30C. to about 80C.being preferred. The pressure employed in the epoxidation can range fromsubatmospheric to superatmospheric with atmospheric being preferred.

The following examples will more fully illustrate the process and the2-vinyl and 2-epoxyethylbicyclo- [2.2.l]hept-5(6)-yl compounds of thisinvention.

EXAMPLE I 2-Vinylbicyclo[2.2. 1 ]hept-5(6)-yl For-mate CR CH HCOO Amixture of 120 grams of 2-vinylbicyclo[2.2.l ]hept- 5-ene and 180 gramsof 98 per cent formic acid was refluxed for 4 hours and then distilledto give 98 grams of 2-vinylbicyclo[2.2.1]hept-5(6)-yl fonnate, b.p. /l0mm., n 30/D 1.4756.

Analysis Calculated for C H O C, 72.26; H, 8.49. Found C, 72.48; H,8.62.

EXAMPLE [I 2-Epoxyethylbicycl[2.2. 1 ]hept-5( 6)-yl Formate To 100 gramsof 2-vinylbicyclo[2.2.l]hept-5(6)-y1 forrnate, prepared as in Example I,which was maintained with stirring at 40C., there was added dropwiseover a 2 hour period 223 grams of a 25.6 per cent solution of peraceticacid in ethyl acetate. After an additional 2 hours at 60C. the reactionwas complete as indicated by a titration for unreacted paracetic acid.The solution was freed of volatiles by codistillation with 400 grams ofethylbenzene and the residue was distilled through a shortcolumn to give98 grams of 2-epoxyethylbicyclo[2.2.1]hept-5(6)-yl formate. A hearts cuthad the following properties: b.p. 87/0.35 mm., n 30/D, 1.4827.

Analysis Calculated for C H O C, 65.93; H, 7.69. Found C, 66.12; H,7.63.

EXAMPLE III 2-Viny1bicyclo[2.2. l ]hept-5(6)-yl Chloride The additionof. 222 grams of 2-vinylbicyclo[2.2.l]- hept-S-ene to 444 grams ofconcentrated hydrochloric acid at 25C. was followed by a slightlyexothermic reaction which raised the temperature to 50C. over a periodof 90 minutes. After this reaction had subsided, the mixture was heatedto 60C. for an additional 90 minutes and then allowed to cool. Theorganic layer was diluted with a little toluene, washed with dilutesodium hydroxide solution, dried over sodium sulfate, and distilled.There was obtained 172 grams of 2-vinylbicyclo[2.2.l]hept5(6)-ylchloride, Redistilled material had the following properties: b.p. 79/ 11mm., n 30/D 1.4935.

Analysis Calculated for C H CI: C, 69.01; H, 8.36. Found C, 69.24; H,8.06.

EXAMPLE IV 2-Epoxyethylbicyclo 2. 1 l ]hept-5 6 )-yl Chloride To 94grams of 2-vinylbicyclo[2.2.1]hept-5(6)-yl chloride, prepared as inExample III, which was maintained with stirring at 55 to 60C., there wasadded dropwise over a period of 2 hours and 15 minutes 222 grams of a24.8 per cent solution of peracetic acid in ethyl acetate. After anadditional 3 hours at 57C., 95 per cent of the theoretical amount ofperacetic acid had been consumed. After standing overnight at C. thesolution was freed of volatiles by co-distillation with ethylbenzene anddistilled through a short column to give 89 grams of2-epoxyethylbicyclo[2.2. l ]hept- (6)-yl chloride, b.p. 75/1 mm., n /D1.4998. The product had an indicated purity of 95.5 per cent by epoxideanalysis (pyridine hydrochloride method).

EXAMPLE V 2-Vinylbicyc1o[2.2.1 ]hept-S 6)-yl lsothiocyanate A mixture of120 grams of 2-vinylbicyclo[2.2. l ]hept- S-ene, 75 grams of water, and76 grams of ammonium isothiocyanate was stirred and heated at 98C. while100 ml.. of concentrated hydrochloric acid was added dropwise over aperiod of 1 hour. After an additional 3 hours at 90C., the mixture wascooled and filtered. The organic layer was separated, 100 ml. of ethylether being added to facilitate layer separation, and distilled througha short column to give 89 grams of 2-vinylbicyclo[2.2.1 ]hept-5(6)-ylisothiocyanate, b.p. 87 to 89l2mm.

Analysis Calculated for C H NS: C, 67.02; H, 7.31. Found C, 66.82; H,7.37.

EXAMPLE V1 2-Vinyl-5(6)-Allyloxybicyclo[2.2.1 ]heptane A mixture of2-vinylbicyclo[2.2.1]hept-S-ene (240 grams), allyl alcohol (348 grams),and boron trifluorideetherate (40 grams) was heated at reflux for 4hours. The kettle temperature was 94C. at the start and 97C. at the endof the reaction. The reaction mixture was cooled, washed successivelywith 200 ml. of water, 200 ml. of 5 per cent aqueous sodium hydroxidesolution, and 200 ml. of water, dried over sodium sulfate and distilledunder reduced pressure. There was obtained 255 grams of2-vinyl-5(6)-allyloxybicyclo[2.2.l]hepta.ne, b.p. 83l5 mm., n 30/D1.4773.

Anal. Calcd for C H O: C, 80.85; H, 10.18. Found C, 80.91; H, 10.31.

EXAMPLE VII 2-Epoxyethylbicyclo[2.2. 1 ]hept-5(6)-yl Glycidyl Ether To202 grams of 2-vinyl-5(6)=allyl oxybicyclo[2.2. 1 heptane, prepared asin Example Y1, which was main= tained with stirring at 60 to 65C., therewas added dropwise over a period of 2 /2 hours 888 grams of a 24.3 percent solution of peracetic acid in ethyl acetate. After an additional 3hours at about 60C., over 97 per cent of the theoretical amount ofperacetic acid had been consumed. The volatiles were removed byco-distillation with 'ethylbenzene and the residue was fracfionallydistilled through an 8 inches X 32 mm. glass helicespacked column togive 35 grams of the monoepoxides, b.p. 68 to 97/0.1 mm., n 30/D14848-14867, and grams of 2-epoxyethylbicyclo[2.2.l]hept-5(6)-ylglycidyl ether. The hearts cut had the following properties: b.p.1l1/0.13 mm., n 30/D 1.4887.

Anal. Calcd for C H O C, 68.54; H, 8.63. Found: C, 68.81; 68.81; H,8.67.

EXAMPLE VIII 2-Vinylbicyclo 2 .2. 1 ]heptan-S 6 )-ol n ca,

A mixture of 333 grams of 2-vinylbicyclo[2.2.1] hept-S-ene, 300 grams ofconcentrated sulfuric acid, and 900 grams of water was stirred andrefluxed for 3 hours. The mixture was allowed to cool and the organiclayer was separated and washed successively with water, 5 per centaqueous sodium bicarbonate solution, and water. After drying over sodiumsulfate, the product, 361 grams, was distilled through a short column togive 58 grams of 2-vinylbicyclo[2.2.1]hept-5-ene, 67 grams of mids-cut,53 grams of 2-vinylbicyclo[2.2.l]- heptan-5(6)-ol, and 86 grams ofhigher boiling material. For comparison purposes, pure2-vinylbicyclo[2.2.l ]heptan-5(6)-ol was prepared by saponification ofthe corresponding formate and was found to have the followingproperties: b.p. 60 61/0.35 mm., n 30/Dl.4970.

Anal. Calcd for C H O: C, 78.21; H, 10.21. Found: C, 78.49; H, 10.17.

EXAMPLE IX 2-Epoxyethylbicyc1o 2.2. 1 ]heptan-S 6 )-ol To 337 grams of2-vinylbicyclo[2.2.1]heptan-5(6)- 01, prepared as in Example V111, whichwas maintained with stirring at 50C., there was added dropwise over aperiod of 3 hours 1106 grams of a 20.6 per cent solution of peraceticacid in ethyl acetate. After an addi tional 3 hours at 50C., 97.6 percent of the theoretical amount of peracetic acid had been consumed.After standing overnight at 0C. the solution was freed of volatiles bycodistillation with ethylbenzene. Distillation of the residue gave 294grams of 2-epoxyethylbicyclo[2.2.l]heptan-5(6)-ol; b.p. 9299C./.4 mm. Ahearts cut of this material had an indicated purity of 97.2 per cent byepoxide analysis (hydrogen bromidedioxane method).

EXAMPLE X l Ethylene Glycol Bis(2-vinylbicyclo[2.2.1 ]hept-5(6)-yl EtherEthylene glycol'(62 grams) and boron trifluorideethl5 erate (9 grams)were heated at 120C. while 2-vinylbicyclo[2.2.1]hept-5-ene (360 grams)was added dropwise over a period of 2 hours. After an additional 4 hoursat 120C., the catalyst was neutralized with 20 grams of sodium carbonatein 100ml. of water. The reaction mixture was dissolved in 300 ml. ofbenzene, washed with 200 ml. of water, and flash distilled to give 144grams of overhead product. Redistillation of the flashed product throughan 8 X 1 inch glass helices- 5 packed column gave 20 grams of ethyleneglycol mono- 2-vinylbicyclo[2.2.l]hept-5(6)-yl v ether. b.p. 75-80/0.25mm. and 96 grams of ethylene glycol bis(2-vinylbicyclo[2.2.l]hept-5(6)-yl ether, b.p 140/0.25 mm.

,Anal. Calcd for C H O C, 79.50; H, 9.99. Found: C, 80.01; H, 10.01.

EXAMPLE XI oca ca o To 92 grams of ethylene glycol bis(2-vinylbicy- 5clo[2.2.l]hept-5(6)-yl) ether, prepared as in Example X, which wasmaintained with stirring at 60C., there was added dropwise over a periodof 100 minutes 248 grams of a 24.2 per cent solution of peracetic acidin ethyl acetate. After an additional 3 hours at 60C., 96 per cent ofthe theoretical amount of peracetic acid had been consumed. Thevolatiles were removed by co-distillation with ethylbenzene and theresidue product, thus obtained, was distilled through a short column togive grams of ethylene glycolbis(2-epoxyethylbicyclo[2.2.1]hept-5(6)-yl) ether, b.p. 1.91/ O.25 mm, n30/D 1.5050.

Anal. Calcd for C H O C, 71.82; H, 9.04. Found: C, 72.06; H, 8.87. I

7 EXAMPLE X11 I 2-Vinylbicyclo[2.2.l ]hept-5(6)-yl Acrylate o u CH CH Aflask containing acrylic acid (288 grams), hydroquinone (5.3 grams) andboron trifluoride etherate 5.3 grams) was maintained at C. while2-vinylbicyc1o[2.2.1]hept-5-ene (240 grams) was slowly added to themixture. The reaction mixture was maintained at 75C for 2 hours afterthe addition of 2-viny1bicyll=CH clo[2.2.1]hept-5-ene had beencompleted. Benzene (550 cc.) was added and the resultant solution waswashed with water. Additional hydroquinone (5.3 grams) was added and theproduct was distilled through a short Vigreux column. In order tominimize polymerization during distillation, nitric oxide was introducedinto the system through a capillary ebullator. There was thus obtainedgrams (35 per cent) of 2-vinylbicyclo[ 2.2.1 ]hept-5(6)-yl acrylate;b.p. 63-66C.'/0.1 mm, n 30/D 1.4844-14850.

Anal. Calcd for C H O C, 74.97; H, 8.39. Found: C, 75.06; H, 8.46.

Saponification equivalent Calcd for C H O 192.

Found: 196.

CH B CH-C- The 2-vinylbicyclo[2.2.1]hept-5(6) -yl acrylate (.69 mole),prepared in Example X11, and 2,6-dinitro-4- chlorophenol (1.3 grams)were charged to a flask fitted with stirrer, condenser, dropping funneland thermometer. The, temperature of the reaction mixture was maintainedat 50C. while a solution of peracetic acid (.76 mole) in ethyl acetatewas added dropwise to the diolefin. Addition of the peracetic acidrequired 2 hours. The reaction mixture was then maintained at 50C. foran additional 5 hours. At the end of this time, 91 per cent ofzthetheoretical amount of peracetic acid had been consumed. The volatileswere removed by co-distillation with ethylbenzene and the residue wasvacuum distilledthrough a short packed column, In order to minimizepolymerization during distillation, nitric oxide wasintroduced into thesystem through a capillary ebullator. There was thus obtained 60 grams(42 per cent) of the epoxyacrylate; b.p. 88-93C./0.1 mm., n 30/D14896-14908.

The infrared spectrum of this material was consistent with the assignedstructure. Analysis: purity by HBrdioxane method 98.9 per cent (assumingone equivalent of HBr is consumed by addition to the double bond of theacrylate group and a second equivalent is consumed by addition to theepoxide).

19 Calcd for C H O C, 69.21; H, 7.74. Found: C, 68.98; H, 7.83.

EXAMPLE XIV A flask containing methacrylic acid (200 grams),hydroquinone (4.8 grams) and boron trifluoride etherate (4.8 grams) wasmaintained at 75C. while 2-vinylbicycle[2.2.1]hept-5-ene (270 grams) wasslowly added to the mixture. The reaction mixture was maintained at 75C.for 2 hours after the addition of 2-vinylbicyclo[2.2.1]hept-5-ene hadbeen completed. Benzene (500 cc.) was added and the resultant solutionwas washed with water. Additional hydroquinone (4.8 grams) was added andthe product was distilled through a short Vigreux column. In order tominimize polymerization during distillation, nitric oxide was introducedinto the system through a capillary ebullator.

Redistillation of the above material through a short packed column gave89 grams (19 per cent) of 2-vinylbicyclo-[ 2.2.1]hept-5(6)-ylmethacrylate; b.p. 6869C./0.2 mm.; n 30/D 1.4818-1.4822.

Anal. Calcd forC H o C, 75,69; H, 8.80 Found: C, 75.37; H, 8.73.Saponification equivalent Calcd for CHI-[1302: Found:

EXAMPLE XV' 2-Epoxyethylbicyclo[ 2.2. l ]hept-5( 6)-yl Methacrylate CH3,o ca ca c11 0-0 2 The 2-vinylbicyclo[2.2.1 ]hept-(6)-yl methacrylate(1.12 moles), prepared as in Example XIV, and 2,6-dinitro-4-chlorophenol (2.3 grams) were charged to a flask fitted withstirrer, condenser, dropping funnel aand thermometer. The temperature ofthe reaction mixture was maintained at 50C. while a solution ofperacetic acid (1.23 moles) in ethyl acetate was added dropwise to thediolefin. Addition of the peracetic acid required 2.25 hours. Thereaction mixture was then maintained at 50C. for an additional 6.5hours. At the end of this time 92 per cent of the theoretical amount ofperacetic acid had been consumed. The volatiles were removed bycodistillation with ethylbenzene. An additional amount (2.3 grams) of2,6-dinitro-4-chlorophenol was added to the residue which was thenvacuum distilled through a short packed column. In order to minimizepolymerization during distillation, nitric oxide was introduced into thesystem through a capillary ebullator. There was thus obtained 100 grams(40 per cent) of the epoxymethacrylate; b.p. 94 .100C./- 12-025 mm., n30/D 1.4870-1.4893. The infrared spectrum of this material wasconsistent with the assigned structure. Analysis; purity byI-IBr-dioxane method 94.8 per cent (assuming one equivalent of HBr isconsumed by addition to the double bond of the methacrylate group and asecond equivalent is consumed by addition to the epoxide).

Anal. Calcd for C H O C, 70.24; H, 8.16. Found: C, 69,58; H, 8.10.

EXAMPLE XVI Bis( 2-Vinylbicyclo 2 2. 1 ]hept-5 6 )-yl) Ether ca ca Aflask containing 2-vinylbicyclo[2.2. l ]heptan-5(6)- 01 (276 grams),prepared as in Example VIII, and boron trifluoride etherate (28 grams)was heated to C. and 2-vinylbicyclo-[2.2.1]hept-S-ene (288 grams) wasadded slowly to the mixture. It soon became apparent that polymerformation was going tobe excessive at 100C., so the temperature waslowered to 80C. The reaction mixture was maintained at 80C. for 3%hoursafter the addition of 2-vinylbicyclo[2.2.l- ]hept-5-ene had beencompleted and was then allowed to stand overnight at room temperature.Benzene 500 cc.) was added and the resultant solution was washed withwater and then with dilute aqueous sodium hydroxide. The product wasflash distilled to separate it from polymer and was then redistilled togive 209 grams (41 per cent) of bis-2-vinylbicyclo[2.2.l]hept- 5(6)-ylether; b.p. 1061l0C./0.3 mm.; n 30/D 15080-15092.

Anal. Calcd for C H O; C, 83.66; H, 10.10. Found: C, 83.74; H,9:95.Iodine Number Ca1cdforC 8H26O;

196.5. Found: 212.

EXAMPLE XVII Bis( 2-epoxyethylbicyc1o 2.2. l ]hept-5 6 )-y] Ether Thebis(2-vinylbicyclo[2.2.1]hept-5(6)-yl) ether (.70 mole), prepared as inExample XVI, was charged to a flask fitted with stirrer, condenser,dropping funnel and thermometer. The temperature of the reaction mixturewas maintained at 50C. while a solution of peracetic acid (1.7 moles) inethyl acetate was added dropwise to the diolefin. Addition of theperacetic acid required 1.15 hours. The reaction was then maintained at50C. for an additional 4.5 hours. At the end of this time 98 per cent ofthe theoretical amount of peracetic acid had been consumed. Thevolatiles were removed by codistillation with ethylbenzene and theresidue was distilled to give grams (82 per cent of the diepoxide; b.p.l75C./0.08 mm., n 30/D 1.5119. Analysis: purity by I-IEr-dioxane method95.0 per cent.

Calcd for C H O C, 74.44; H, 9.03. Found: C, 74.51; H, 9.16.

L ca ca CH2 cu-cr1 2 A flask containing 2,2-dimethyl-4-pentenoic acid(152 grams) and boron trifluoride-etherate (10 grams) was maintained at85C. while 2-vinylbicyclo[2.2. l ]hept-S-ene (144 grams) was addedslowly to the mixture. The reaction mixture was maintained at 80C. forone hour after the addition of 2-vinylbicyclo[2.2.l- ]hept-5-ene hadbeen completed and was then allowed to stand overnight at roomtemperature. The material thus obtained was washed with water and withdilute aqueous sodium hydroxide and was finally distilled. There wasthus obtained 85 grams (29 per cent) of 2-vinylbicyclo[ 2.2. 1 ]-hept-56) yl-2,2-dimethyl-4-pentenoate; b.p. l06C./l.25 mm., n 30/Dl.47081.4722.

Anal. Calcd for C, H O C, 77.37; H, 9.74. Found: C, 77.38; H, 9.78Iodine Number Calcd for C H O 204.5. Found: 203.

EXAMPLE XIX 2-Epoxyethylbicyclo[2.2. l ]hept-5(6)-yl 2,2-Dimethyl- 4,5-Epoxypenten onate CH O /o\ i ll CH l'l- Cll -C C- The2-vinylbicyclo[2.2.l ]hept-(6)-yl 2,2-dimethyl- 4-pentenoate (0.62 mol),prepared as in Example XVIII, was charged to a one-liter flask fittedwith stirrer, condenser, dropping funnel and thermometer. Thetemperature of the reaction mixture was maintained at 50C. while asolution of peracetic acid (1.4 moles) in ethyl acetate was addeddropwise to the diolefin. Addition of the peracetic acid required 2hours. The reaction mixture was then maintained at 50C. for anadditional 9 hours. At the end of this time, 94 per cent of thetheoretical amount of peracetic acid had been consumed. The volatileswere removed by codistillation with'ethylbenzene and the residue wasdistilled to give 43 grams (25 per cent) of the diepoxide; b.p.133-I34C./0.08 mm., n 30/D 14802-14808. Analysis: purity by HBr-dioxanemethod 103 per cent. The infrared spectrum of this material wasconsistent with the assigned structure.

Calcd for C, H O.,: C, 68.54; H, 8.63. Found: C. 67.94; H, 8.72.

EXAMPLE XX 2-VinyIhicycIo[ 2.2.1 ]hept-5( 6 )-yl 2,2-dimethyl-4-pentenylether CH CH CH CH-CH -C A flask containing 2,2-dimethyl-4-pentenol (400grams), boron trifluoride-etherate (64 grams) and hydroquinone (2 grams)was maintained at C. while 2-vinylbicyclo[2.2.l ]hept-S-ene (649 grams)was added slowly to the mixture. This reaction mixture was maintained at80C. for 1 hour after the addition of 2-vinylbicyclo[2.2.l]hept-S-enehad been completed and was then allowed to standovernight at roomtemperature. It was then heated at 100C. for an additional 2 hours,washed with water and with dilute aqueous sodium hydroxide, and finallydistilled. There was thus obtained 376 grams (45 per cent) of2-vinylbicyclo[2.2.l ]hept 5(6)-yl 2,2-dimethyl-4-pentenyl ether; b.p.98-100C./l.4l.5 mm., n 30/D 14700-14710.

Anal. Calcd for C H O: C, 81.99; H, 1 1.18. Found: C, 82.03; H, 11.18.Iodine Number Calcd. for CmHznOI 216. Found: 220.

EXAMPLE XXI 2-Ep0xyethylbicyclo122. l ]hept-S 6 )-y]2,2-Dimethyl-4,5-Epoxypentyl Ether 3 1 ca err cu err-ur ca -o The2-vinylbicyclo[2.2. l .]hept-5(6)-yl 2,2-dimethyl- 4-pentenyl ether (1.1moles), prepared as in Example XX, was chargedto a flask fitted withstirrer, condenser, dropping funnel and thermometer. The temperature ofthe reaction mixture was maintained at 40C. while a solution of theperacetic acid (2.6 moles) in ethyl acetate was added dropwise to thediolefin. Addition of the peracetic acid required 3 hours. The reactionmixture was then maintained at 40C. for an additional 9 hours. At theend of this time 94 per cent of the theoretical amount of peracetic acidhad been consumed. The volatiles were removed by codistillation withethylbenzene and the residue was distilled to give grams (29 per cent ofthe diepoxide; b.p. l28C;/0.03 mm., n 30/D 1.4790. Analysis: purity byHBrdioxane method 86.5 per cent. The infrared spectrum of this materialwas consistent with the assigned structure.

Calcd for C H O C, 72.16; H, 9.84. Found: C, 72.12; H, 9.86

The 2-vinylbicyclo[2.2. l ]hept-5(6)-yl compounds of this invention finda wide variety of uses. Among these are those of solvents for resins andoils, monomers for preparing synthetic waxes and resins, chemicalintermediates for pharmaceuticals, wetting agents, insecticides,emulsifying agents, detergents, bactericides and fungicides.

The 2-vinylbicyclo[2.2.l ]hept-5(6)-yl esters of this invention, e.g.,2-vinylbicyclo[2.2.l]hept-5(6)-yl acrylate, are particularly useful asvehicles in preparing paints, varnishes and similar coating materials.Forthis purpose, they may be admixed with at least one oxidationcatalyst. These oxidation catalysts include peroxides, such as benzoylperoxide, tert. butyl hydroperoxi ide, oraluroyl peroxide, and metallicdriers, such as the oil-soluble salts of heavy metals, typified by lead,cobalt, manganese, and other polyvalent metals supplying siccativeaction, and of carboxylic acids imparting oilsolubility to the salt,including naphthenic acids, longchain fatty acids such as linoleic andlinolenic, and ether acids, such as butoxyacetic or octyloxyaceticacids. Mixtures of peroxides and metallic driers are particularlyefficacious.

When coating compositions comprising the polyesters of this inventionand an oxidation catalyst are applied to surfaces which are then exposedto air and/or heat, they are converted to hard, tough films, which aresubstantially insoluble in all common organic solvents and are highlywater-resistant and nonporous. When used in finishes on metal,exceptional adhesion is obtained, and treated metal sheets finished witha baked coating maay be flexed without cracking or breaking of the film.I

Since the new estersof this invention are compatible withnitro-cellulose as well as with the natural drying oils, for example,linseed, tung, soybean, oiticica, and fish oils, as well as with manynatural and synthetic resins, they may be used for the preparation of awide variety of coating and plastic compositions.

Some of the 2-vinylbicyclo[2.2.l ]hept-5(6)-yl ethers of this invention,e.g., ethylene glycol bis(2-vinylbicyclo[2.2. l ]hept-5(6)-yl ether,possess properties fitting them for a great variety of industrialapplications. Many of these new ethers are also useful as solvents forresins and waxes. High boiling ethers are useful as plasticizers fornatural and synthetic resins and elastomers, including syntheticrubbers, polyvinyl chloride, polyvinyl esters, polystyrene, polyacrylicesters, polymethacrylic esters, copolymers of such materials, rubberhydrochloride, chlorinated rubber, nitrocellulose, celluloseacetate,ethyl cellulose, cellulose acetate-butyrate, etc. Derivatives containingsuch groups as halogen, nitro, cyano, thiocyano, etc., possessinsecticidal action to .a marked degree. Some of the lower ethers havepleasant, flowery odors which recommend them for such uses as scentingsoaps, cosmetics, and the like.

The ethers of this invention possessing a double bond may be reactedwith hydrogen, halogen, thiocyanogen and similar agents to yield newcompounds which are themselves useful as solvents, hydraulic fluids, oiladditives, insecticides, etc. The ethers also react with sulfuric acidto give water-soluble products useful as wetting andpenetrating agents,emulsifiers, and detergents.

The 2-vinylbicyclo[2.2.l]hept-5(6)-yl thioethers of this-invention maybe useful, per se, as insecticides, fungicides, antioxidants, rubbervulcanization accelerators, and as additives for improving petroleumproducts.

Certain 2-epoxyethylbicyclo[2.2.1]hept5(6)-yl compounds of thisinvention are especially useful in the resin art. They are capable ofbeing cured at room temperature with aliphatic amines to give polymersuseful in resin applications. The vicinal epoxides afford relativelyhigh molecular weight resins when cured with polycarboxylic acids.

The following example illustrates the usefulness of a2-epoxyethy1bicyclo[2.2.1 ]hept-5( 6)-yl compound of this invention.

EXAMPLE XXII 2-Epoxyethylbicyclo[ 2 2. l ]hept-S 6 )-yl glycidyl etherresins 2-Epox yethylbicyclo[ 2.2. 1 ]hept-5( 6 )-yl glycidyl ether,prepared as in Example VII, forrns resins readily with both acidic andbasic hardeners. It cures exothermally from room temperature withaliphatic polyamines to give resins with heat distortion points as highas 97C. A heat distortion point of 23 3C. was obtained from2-epoxyethylbicyclo[2.2.1]hept-5(6)-yl glycidyl ether andp,p'-methylenedianiline combination after curing at 200C.

2-Epox yethylbicyclo[ 2.2. 1 ]hept-S 6 )-y] glycidyl ether formed resinsreadily with both acidic and basic hardeners. With the reaction productof 1 mol of diethylenetriamine with 1 mol of ethylene oxide, an aminehardener, Z-epoxyalkylbicyclo 2. 2. 1 ]hept-5( 6 )-yl glycidyl etherreacted exothermally from room temperature; a 25 gram test bar, afterstanding at room temperature for 8 days, had a heat distortion point of97C. After a post-cure of 2 hours at C., this value was increased to106C. and a flexural strength'of 17,940 pounds per square inch wasobserved.

When hardened with para, para'-methylenedianiline,2-epoxyethylbicyclo[2.2. l ]hept-5( 6)-yl-glycidyl ether gave a resinwith heat distortion points of 190C. and 233C. after curing at C. (6hours) and 200C. (4 hours), respectively.

The addition of 2-epoxyethylbicyclo[2.2.1]hept- 5(6)-yl-glycidyl etherto the diglycidyl ether of 2,2- bis(p-hydroxyphenyl)-propane to theextent of 20 per cent of the mixture resulted in a viscosity decrease offrom 1 1,000 to 2,000 centipoises at 25C. This mixture, when hardenedwith the reaction product of 1 mol of diethylenetriamine with 1 mol ofethylene oxide, gave a resin with heat distortion point of 78C. aftercuring for 8 days at room temperature. A post-cure of 2 hours at 120C.raised this value to 90C. The cured resin, when tested for flexuralstrength, yielded at 18,660 psi. without breaking. The resulting testwas (5 X X A inches), after essentially recovering from the flexuraltest, had an Izod impact of 0.8 ft. lb/in. notch.

2-Epoxyethylbicyclo[ 2.2. l ]hept-5( 6 )-yl-glycidyl ether has beenshown to be an amine-reactive diepoxide. The high reactivity and lowviscosity should be useful in applications requiring fast-curing,solventless formulations such as those contemplated for the Gusmer gun.

Although this invention has been illustrated by the preceding examples,it is not to be construed as limited to the materials employed therein,but rather, the invention encompasses the general area as hereinbeforedisclosed. Various modifications and embodiments of this invention canbe made without departing from the spirit and scope thereof.

What is claimed is:

1. Ethers of 2-vinylbicyclo[2.2.1]hept-5(6)-ol of the formula:

CH CH R is selected from the group consisting of alkyl of from 1 to 18carbon atoms, alkenyl of from 2 to 20 carbon atoms, cycloalkyl of from 5to 12 carbon atoms and cycloalkenyl of from 5 to 12 carbon atoms.

2. 2-Vinylbicyclo[2.2.1]hept-5(6)-hydroxyl COm- 3.2-Vinylbicyclo[2.2.l]hept-5(6)-yl compounds of pounds of the formula:the formula :1 a 6 HO CH CH 5 7 Z wherein R is alkenyl of from 2 tocarbon atoms.

1. ETHERS OF 2-VINYLBICYCLO(2,2.1)HEPT-5(6)-OL OF THE FORMULA: 3.2-Vinylbicyclo(2.2.1)hept-5(6)-yl compounds of the formula